Fixing agents for perfumes and other volatile compounds



Patented Aug. 24, 1937 UNITED STATES PATENT OFFICE FIXING AGENTS FOR PERFUMES AND O'IH- v ER VOLATILE COMPOUNDS a corporation of Germany No Drawing. Application April 10, 1934, Serial No. 719,856. In Germany April 11, 1933 14 Claim.

This invention relates to perfumes and fixing agents therefor.

The employment of fixatives is of great importance in connection with the manufacture of 5 perfumed preparations, since perfumes, volatile solutions and the like evaporate relatively quickly I out of the products being impregnated with them, as e. g. commercial and cosmetic soap preparations. There are only a few substances which answer the demands to be expected from a fixing agent. They must satisfy the following requirements; they must possess a good dissolving power for perfumes and a high boiling point and must be either completely odorless or distinguished by a slight, pure individual odor.

It is an object of this invention to produce improved perfumes. An additional object is the provision of improved fixing agents in perfumes and in other substances such as soaps, cosmetics and the like, in which perfumes are used. Additional objects will become apparent from a consideration of the following specification.

These objects are attained according to the present invention by combining with the perfumes high molecular, fatty alcohols of the allphatic or alicyclic series, especially the primary monoand dior polyhydric saturated or unsaturated alcohols having 8 or more carbon atoms in the molecule. The alcohols may be used as such or as components of ethers in which an alcohol of the type indicated is etherified with itself or with another aliphatic or alicyclic alcohol. There are certain advantages inherent in hydroxy ethers and particularly in the ethers wherein the alcohols are etherified with glycerol or polyglycerol. taining at least 8 carbon atoms in the molecule produces a preferred agent for the purposes of the invention but a lower radical as for example the 40 hexyl alcohol radical may be used. The resulting ethers may be used without further change in configuration or they may be esterified, preferably with aliphatic acids, and the esterifled derivatives used in place of or in admixture with unesterified ethers. The aforementioned alcohols or ethers are incorporated in perfumes, soaps, cosmetics, and many similar products, in accordance with the procedure well known to one familiar with the art. Because of 'their solvent power the glycerol ethers, especially the lower molecular ethers, are also useful for extracting perfumes. The quantity of high molecular alco hol used is approximately equal to or more than the quantity of perfume as contrasted with additions of 5% or the like of alcohols to perfumes The etherifying radical con- An excellent adhesive perfume-composition is obtained if 1 part of coumarin is dissolved in 3 parts of octyl alcohol.

. Example 2 An extraordinary soap-perfume is obtained by dissolving 9 parts of oil of turpentine, 1 part of geraniol acetate, 5 parts of bergamot oil and 3 15 parts of dodecyl alcohol.

Example 3 During the manufacture of an pure soap by boiling the best raw materials, 1% lilac (el- 20 der) -composition and oleyl alcohol equal to 10% of the weight of the perfume are added. The

soap obtained is distinguished by an extraordinary. odor-stability, even when stored in open cakes for months. Instead of the oleyl alcohol, a mixture consisting of equal parts of oleyl and stearyl alcohol may be employed with the same good results.

' Example 4 A toilet soap possessing an excellent adhering 30 odor is obtained if 2% of an eau de Colognecomposition is'compounded with 5% of its weight of castor oil alcohol, is added to an 80% ground soap being boiled from good raw materials (beef tallow and coconut oil) before its crushing.

Example 5 A perfume composition prepared from ethereal oils is mixed with 1 to 2 parts of glycerine-monooctyl-ether. A concentrated perfume mixture is 46 obtained, the odor of which is very lasting. The

' capronate of di-hexyl-ether of glycerol or the glycerine-di-naphthenyl-ether is also applicable in the same manner as the glycerine-mono-octylether.

Example 6 Dissolve 20 parts of crystal musk in parts of glycerine mono octa decenyl ether. The odor of the composition obtained is a very mild 5 one and by far less obtrusive than the odor of the musk. The glycerine-mono-octadecenylether may also be substituted by the di-propionate ofmono-cyclo-hexyl-ether or the acetate of mono-lauryl ether of glycerol. 55

Example 7 Add 10% mono-lauryl-ether of glycerine and from 2% to 4% of a synthetic rose blossom oil to a fine toilet soap during its preparation. The soap obtained possesses a very pleasant odor which will be permanent, even if stocked on open shelves for many months. The laminate of didecyl ether of poly-glycerol or the isobutyrate of dicetyl ether of di-glycerol or the di-propionate of di-decyl ether of di-glycerol are applicable in the soap in the same manner as the mono-lauryl-ether of glycerine.

It is to be understood that the aforementioned examples are .illustrative merely of compositions wherein the new ethers and their derivatives described herein are incorporated. These ethers and their esterified derivatives may be incorporated with numerous other compounds in order to produce various cosmetics, soaps, perfumes, and other products of similar nature. Among the compounds falling within this category mention may be made of glycerol, sugar, hydrocarbons, cyclohexanol, butylalcohol, deca-hydronaphthalene, sulfates or sulfonates of higher molecular alcohols and so on.

The ethers comprised herein may be produced by reacting an alkyl sulfuric acid with glycerine or polyglycerine in an alkaline medium. These compounds may likewise be produced by reacting an alkyl chloride with sodium-glyceroxide or sodium-poly-glyceroxide. If the higher molecular products are to be produced the alkyl radical of the alkyl sulfuric acid ester or of the alkyl chloride should contain at least 8 carbon atoms. In place of the aforementioned ethers wherein the etherifying radical'is the residue of an allphatic compound there may be similarly produced ethers wherein the etherifying radical is the residue of an alicyclic compound.

In producing high molecular ethers of glycerol and/or polyglycerol wherein the etherifying.

radical is an aliphatic compound this radical should contain at least 8 carbon atoms and preferably should be a straight chain aliphatic radical containing from 8 to 18 carbon atoms. These etherifying radicals may be either saturated or unsaturated, in many cases a mixture of compounds containing saturated and unsaturated etherifying radicals producing very satisfactory results. Among etherifying radicals falling within this category mention may be made of octyl, nonyl, decyl, octadecyl, lauryl, myristyl, cetyl, oleyl and ricinoleyl. As previously mentioned, in place of the aliphatic etherifying group an alicyclic radical may be used. Alicyclic radicals which are typical of this class are cyclopentyl, cyclohexyl, methyl cyclohexyl, naphthenyl, abietyl and hydroabietyl. It is to be understood that this invention comprises the production of polyethers of glycerol or polyglycerol wherein the resulting ethers may contain more than one of the aforementioned alicyclic radicals, or a mixture of the aforementioned aliphatic and alicyclic etherifying radicals or the aforementioned aliphatic and/or alicyclic etherifying radicals in addition to other etherifying radicals which may contain less than 8 carbon atoms in the group.

It is frequently advantageous to etherify the glycerol or polyglycerol with a mixture of alcohols or their derivatives. For example, the mixture of alcohols derived by the sodium or catalytic reduction of cocoanut or palm kernel oil may be utilized in producing products coming within the scope or this invention. These cocoanut or palm kernel alcohols contain large portions of lauryl alcohol as well as lower and higher members of the fatty alcohol series. Very satisfactory results may be obtained by removing those members of the series lower than lauryl alcohol and utilizing the higher alcohols having not less than 12 carbon atoms, and particularly alcohols having from 12 to 18 carbon atoms, in the production of the aforementioned ethers. However, it is to be understood that those alcohols lower than lauryl alcohol are contemplated for use according to the instructions given herein. In place of alcohols obtained from cocoanut and palm kernel oils mixture of alcohols, the compositions of said mixtures being determined according to the boiling points of the individual components, derived from other natural sources may be substituted. Alcohols derived from natural sources contemplated herein are for instance those from sperm oil, Montan wax, castor oil, wool fat, beeswax, etc. In this connection it may be stated that alcohols containing a mixture of saturated and unsaturated constituents are frequently quite advantageous. Alcohols from sperm oil contain the unsaturated oleyl constituent as well as the saturated stearyl and cetyl constituents, consequently they may advantageously be used in producing ethers of glycerol and polyglycerol. In place of the aforementioned mixture of saturated and unsaturated alcohols mixtures of alcohols containing other saturated and/or unsaturated constituents as well as varying proportions of these components may be selected.

The aforementioned ethers may be utilized by incorporation with various compounds containing perfumes or other volatile ingredients to be fixed therein. They may also be used as solvents for extracting perfumes and the like from raw materials. Likewise, these ethers may first be esterified and then incorporated with the usual components. The esteriiying constituent is preferably an aliphatic monocarboxylic acid. Representative examples of such-acids are acetic, propionic, butyric, isobutyric, crotonic, lactic, levulinic, caproic, lauric, oleic, methoxyacetic, ricinoleic, stearic, myristic, elaidic, eleostearic, as well as mixtures of fatty acids. Suitable mixtures of fatty acids are mixtures of the aforementioned in varying proportions as well as mixtures of the various other acids which would occur to one skilled in the art from a consideration of the aforementioned well known acids. Furthermore, the mixture of acids occurring in natural substances may be utilized, for instance those mixtures of acids obtained from oils and fats such as cocoanut oil, wool fat, etc. In general, it is preferable to introduce not more than one esterifying radical into the ether of glycerol or polyglycerol. However, it is to be understood that in its broadest scope this invention comprises the introduction of more than one esterifying radical into said ethers. In the event that more than one esterifying radical is introduced into the ethers described herein the first esterifying radical should advisably be selected from among the aforementioned acids and the remaining esteriiying radical or radicals may be selected from the same acids or from other and quiteunrelated acids. The means of producing esters are well known and may be exemplified by reacting the etherified glycerol or polyglycerol or mixtures of the same with the desired acids in the presence of an agent having an avidity for water such as sulfuric or phosphoric acid.

The mono-ethers of glycerol and poly-glycerols are preferred, but the di-ethers may be used. The mono-ethers have the advantage that they are easily soluble in ethereal oils. The di-ethers have the advantage that they have a wax-like character and a high boiling point. The mono-ethers described are liquid, intermediate or solid as the alcohol components are low or high molecular.

The low molecular ethers are more liquid and therefore preferable for purposes where fluidity is desired.

With the help of these the most various synthetic or natural perfumes can be rendered soluble, so that they may be employed in connection with the manufacture of perfume composi- 16 tions. They are also useful in the extraction of natural or synthetic perfumes and other similar compounds. These ethers are products of a high boiling point, which even in the smallest quantity have the ability to fix perfume substances.

SODissolved perfumes and volatile solution agents are released by them extremely slowly and gradually, since they reduce the vapor pressure of these substances quite considerably. The odor of the perfumes added is bound in the compound 25 to such an extent that the same, ven if present in high concentrations, is a pleasant one. The individual odor of the ether, if present at all, is extremely weak and pleasant and easily masked by the odor of the perfumes added. In contrast 30 with ester-like substances, which have already been suggested for similar purposes and which under hydrolytic influences are inclined to saponify, they have the advantage that, owing to their ether structure, they are extraordinarily stable.

35 In contrast with fixing agents heretofore used unpleasant after odor is not to be noticed after I evaporation. The higher molecular solid ethers are particularly preferred in the manufacture of soaps, salves, creams, polishing substances and the like. These products are applied in a manner customary for fixing agents. These compounds can be used alone as well as in mixtures, and if desired may be combined with usual fixatives.

As many apparently widely diflerent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

For further disclosure of the features and advantages of this invention reference should be made to applicant's co-pending applicationfiled of even date herewith.

I claim:

1. A perfumed composition containing a perfume and a fixing agent consisting of a monoalkyl-ether of glycerol.

2. A perfumed composition containing a perfume and a fixing agent consisting of an ether of aliphatic alcohol having 1 to 8 carbon atoms in the molecule and a glycerol.

3. A perfumed composition containing a perfume and a fixing agent consisting of an ether of aliphatic alcohol having at least 8 carbon atoms in the molecule and 9. glycerol.

4. A perfumed compositioncontaining a perfume and a fixing agent consisting of an ether of an alicyclic alcohol and a glycerol.

5. A perfumed composition comprising a perfume and a fixing agent consisting of an esterified derivative of an ether of alcohols of the group consisting of aliphatic, alicyclic and naphthenic alcohols and glycerol and polyglycerol.

6. A composition as defined in claim 3 in which the alcohol is a straight chain alcohol.

'7. A perfumed composition containing a-perfume and as a fixing agent an ether of a fatty alcohol having 8 or more carbon atoms in the molecule and a glycerol.

8. A perfumed composition containing a perfume and as a fixing agent a carboxylic acid ester of an ether of an alcohol of the group consisting of the primary aliphatic alcohols having 12 to 18 carbon atoms in the molecule and alicyclic alcohols.

9. A perfumed composition containing a perfume and, as fixing agent, an ether of a primary aliphatic alcohol having 8 or more carbon atoms in the molecule.

, f 10. A perfumed composition containing a perfume and, as fixing agent, an ether of a primary aliphatic alcohol having 8 or more carbon atoms in the molecule and a glycerol.

11. Aperfumed composition containing a perfume and, as fixing agent, a mono ether of a primary aliphatic alcohol having 8 or more carbon atoms in the molecule and a glycerol.

12. A perfumed composition containing a perfume and, as fixing agent, an ester of an ether of a primary aliphatic alcohol having 8 or more carbon atoms in the molecule with an aliphatic mono-carboxylic acid.

13. A perfumed composition containing a perfume and, as fixing agent, an ester of an ether of a primary aliphatic alcohol having 8 or more carbon atoms in the molecule and a glycerol with an aliphatic mono-carboxylic acid.

14. A perfumed composition containing a perfume and a fixing agent of the group consisting of ethers formed by alcohols of the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, and the alicyclic alcohols of the group consisting of naphthenic, abietyl and hydro-abietyl alcohols, the glycerol and poly-glycerol ethers of said alcohols and the carboxylic acid esters of said ethers.

WALTHER SCHRAU'I'H. 

